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EP3684856A1 - Membrane de toiture - Google Patents

Membrane de toiture

Info

Publication number
EP3684856A1
EP3684856A1 EP18785525.9A EP18785525A EP3684856A1 EP 3684856 A1 EP3684856 A1 EP 3684856A1 EP 18785525 A EP18785525 A EP 18785525A EP 3684856 A1 EP3684856 A1 EP 3684856A1
Authority
EP
European Patent Office
Prior art keywords
plasticizer
roofing membrane
ester
carbodiimides
carbodiimide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP18785525.9A
Other languages
German (de)
English (en)
Other versions
EP3684856B1 (fr
EP3684856B8 (fr
Inventor
Udo Simonis
Johannes Glück
Ute FRANKE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bmi Deutschland GmbH
Original Assignee
BMI Technical Services GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BMI Technical Services GmbH filed Critical BMI Technical Services GmbH
Priority to EP20184501.3A priority Critical patent/EP3766928A1/fr
Publication of EP3684856A1 publication Critical patent/EP3684856A1/fr
Publication of EP3684856B1 publication Critical patent/EP3684856B1/fr
Application granted granted Critical
Publication of EP3684856B8 publication Critical patent/EP3684856B8/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
    • E04D5/06—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of plastics
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
    • E04D5/10—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of compounded or laminated materials, e.g. metal foils or plastic films coated with bitumen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers

Definitions

  • the invention relates to a roofing membrane. Furthermore, the invention relates to a method for producing a starting mixture for producing a roofing membrane. The invention also relates to the use of a plasticizer.
  • Sealing membranes in particular roofing membranes usually contain a base polymer based on polyvinyl chloride (PVC), polyvinyl chloride copolymers, ethylene-vinyl acetate terpolymers, ethylene-vinyl acetate copolymers (eg ethylene / n-butyl acrylates / carbon monoxide or ethylene / vinyl acetate / carbon monoxide) and a Plasticizer that has sufficiently good softening effect. It should also be ensured in the selection that, in addition to the large number of other requirements, a particular resistance to water media is given.
  • PVC polyvinyl chloride
  • ethylene-vinyl acetate terpolymers ethylene-vinyl acetate copolymers
  • ethylene-vinyl acetate copolymers eg ethylene / n-butyl acrylates / carbon monoxide or ethylene / vinyl acetate / carbon monoxide
  • Plasticizer that has sufficiently good softening effect
  • ester-based plasticizers for example, phthalic acid esters or polyester-based polymer plasticizers, e.g. B. based on adipic acid or sebacic acid as a polymeric plasticizer hydrolysis is possible.
  • the long-chain plasticizers are degraded to the starting materials alcohol and dicarboxylic acid, with the result that a migration of the degradation or hydrolysis products to the surface of the roofing membrane occurs.
  • the concentration of the softening component decreases, resulting in a reduction in the flexibility of the roofing sheet.
  • hydrolysis stabilizers - which are H + ions / proton scavengers - can be used to improve degradation by hydrolysis.
  • phthalic acid esters are used as plasticizers for non-bitumen-compatible waterproofing membranes on a large scale. Again, the mechanism of hydrolysis is known.
  • WO 20017/096356 AI relates to a plastic film comprising a mixture of polyvinyl chloride (PVC) and at least one thermoplastic polyurethane and their use for sealing or lining of containers for storing or conveying biodiesel.
  • PVC polyvinyl chloride
  • thermoplastic polyurethane exclusively films are described without any reference to a roofing membrane.
  • the CH 55 10 944 relates to a process for the preparation of thermoplastically processable plastic mixtures based on polyurethane-polyvinyl chloride, wherein polyvinyl chloride initially with the required for the preparation of the polyurethane starting materials intensively below the reaction temperature of not and then gradually in the heat to a polyvinyl chloride containing thermoplastic convertible polyurethane.
  • CH 55 10 944 only films and test plates are described without any reference to a roofing membrane.
  • the invention essentially provides a roofing membrane comprising a base polymer, an ester-based polymer plasticizer and at least one hydrolysis stabilizer containing at least one carbodiimide.
  • the free acid groups of the carboxylic acid are completely converted by the polymerization into an ester group.
  • These free acid groups are characterized by the so-called "acid number.”
  • the acid value can be described insofar as it covers all acidic functions that can be neutralized by potassium hydroxide solutions.
  • Ester based plasticizers e.g. B. polyester-based polymer plasticizers are endangered by acid-catalytic hydrolysis.
  • the degradation of the polymer plasticizer depends on the acid number of the starting product, i. H. of the polymer plasticizer, from. Experiments have shown that the degradation of the plasticizer takes place more quickly the higher the acid number of the starting product.
  • ester-based polymer plasticizers have an acid number of 0.1-1, preferably 0.3-0.5.
  • polyester-based plasticizer in particular based on adipic or sebacic acid, is used.
  • the starting materials used for the polyester-based plasticizer in% by weight are:
  • Dicarboxylic acid 52.0 ⁇ 6.6, preferably 55.4 ⁇ 3.0, more preferably 57.1 ⁇ 1.9
  • Neopentyl glycol 22.0 ⁇ 20.0, preferably 15.0 ⁇ 7.0, more preferably 14.1 t 2.1 further diol 13.3 ⁇ 12.0, preferably 18.1 ⁇ 6.0, most preferably 17 , 3 ⁇ 2.9
  • Alcohol mixture 12.7 ⁇ 11.0, preferably 1 1, 5 ⁇ 6.0, more preferably 1 1.5 ⁇ 2.3 wherein the total is 100.
  • starting raw materials in wt .-% of adipic acid or sebacate is: at least one dicarboxylic acid from the group adipic acid, sebacic acid
  • the end cap may be isononanol or isodecanol.
  • isononanol and isodecanol can each be an isononal or isodecanol mixture.
  • isononanol consist predominantly of 1-nonanol, monomethyloctanols, dimethylheptanols and monoethylheptanols.
  • hydrolysis stabilizer contains at least one carbodiimide, a significant improvement in the hydrolysis resistance is given, while at the same time the essential properties remain unchanged compared to sealing membranes that do not contain a corresponding hydrolysis stabilizer.
  • the proportion in% by weight of the hydrolysis stabilizer containing the at least one carbodiimide is 0.1-5, in particular 0.5-2.
  • thermal stabilizer in addition to the at least carbodiimide-containing hydrolysis stabilizer, a thermal stabilizer is included.
  • thermal stabilizer in particular based on Ca / Zn one-pack stabilizers, Ba / Zn or an organic heat stabilizer such as OBS ® the company Chemson in question.
  • a one-pack Ca / Zn stabilizer is preferably composed of a) Ca / Zn (from stearates, octoates, behenates, carboxylates) with Ca / Zn in the ratio
  • hydrotalcites are characterized by a particularly low water absorption and increased stability.
  • Lubricants are included to the extent to provide processing aid to equipment.
  • Antioxidants increase the thermal stability.
  • Flow aids serve as incorporation and dispersion aids.
  • the at least one carbodiimide is selected from the group consisting of monomeric aliphatic carbodiimides, oligomeric aliphatic carbodiimides, polymeric aliphatic carbodiimides, monomeric aromatic carbodiimides, oligomeric aromatic carbodiimides and polymeric aromatic carbodiimides.
  • the present invention accordingly also relates to a process for producing a roofing or sealing membrane, wherein the composition contains at least one carbodiimide selected from the group consisting of the monomeric aliphatic carbodiimides, oligomeric aliphatic carbodiimides and polymeric aliphatic carbodiimides.
  • the molar ratio of added carbodiimide groups to the initial acid content of the ester used can vary within wide ranges and, according to the invention, is preferably in the range from 20: 1 to 1:10, preferably from 10: 1 to 1: 2. in that the molar ratio of added carbodiimide groups to the initial acid content of the ester used is in the range from 20: 1 to 1:10.
  • the roofing or sealing membrane comprises a base polymer, a polymeric plasticizer based on an adipic acid or sebacic acid polyester having an average molecular weight of 3,000 to 12,000 and / or a monomeric plasticizer, for example based on phthalic acid esters, and / or a polyacrylate and / or a rubbery polymer which preferably consists of (a) 40 to 80, preferably 50 to 80 and in particular 55 to 75 wt .-% butyl acrylate or optionally a mixture of butyl acrylate and 2-ethylhexyl acrylate containing up to 40 wt .-% 2-ethylhexyl acrylate, (b ) from 5 to 35, preferably from 5 to 20 wt .-% of at least one substance from the group consisting of methyl methacrylate, ethyl methacrylate, methyl acrylate or ethyl acrylate (c) from 4 to 30, preferably 6 to 30,
  • base polymer polymers which are commonly used to make geomembranes.
  • polyvinyl chloride (PVC) or polyvinyl chloride copolymers are used as base polymers. Mixtures of these are also usable.
  • the base polymer is used, for example, in proportions of from 20 to 60% by weight, preferably from 35 to 55% by weight. All data in% by weight refers to the entire composition.
  • the adipic acid or sebacic acid polyester is used, for example, in proportions of from 20 to 45% by weight, preferably from 25 to 35% by weight.
  • Sealing sheets of compositions with such proportions of adipic acid or sebacic acid polyester have a particularly good compatibility with bitumen and polystyrene as well as a high migration stability even at elevated temperatures. Also, high notched impact strength and high impact toughness are listed as a positive characteristic. The tensile impact strength is determined on the basis of DIN EN ISO 8256 and DIN 53453.
  • composition for producing a geomembrane may contain a polyacrylate.
  • polyacrylates include, for example, ethyl-butyl acrylate, butyl acrylate, copolymers of acrylic acid and vinyl chloride, MMA or PMMA.
  • the polyacrylate component contributes significantly to improving the aging and weathering resistance of the geomembranes and is mainly used in two-layer or multi-layer systems in the topsheets.
  • the use of butyl acrylate is particularly preferred.
  • the polyacrylate may be used in the form of PMMA or MMA coated butyl acrylate particles.
  • These butyl acrylate particles preferably have an average particle size of 100 ⁇ or less, most preferably the average particle size is between 5 and 40 ⁇ .
  • Another polyacrylate is a copolymer of acrylic acid with vinyl chloride, especially a graft copolymer of these compounds.
  • Such graft copolymers are preferably used as granules having a particle size between 0.25 and 5 mm, more preferably between 1 and 2 mm.
  • the polyacrylates used have an average molecular weight of 5,000 to 120,000, preferably from 10,000 to 100,000.
  • the polyacrylates used are used in the compositions, for example in proportions of 3 to 30 wt .-%, preferably from 8 to 25 wt .-%, in particular 10 to 20 wt .-%. Sealing sheets of compositions with such proportions of polyacrylates have a particularly high resistance to aging and can also be processed very well at low temperatures. Particularly preferred is the use of the marketed under the trade name Sunigum ® Goodyear or Omnova Solutions rubbery polymer. In the roof sheets of the invention, the polymer is used in amounts of 1 to 30, preferably 5 to 20 and in particular 8 to 15 wt .-%.
  • the adipic acid polyester is in particular composed of adipic acid and 1,4-butanediol. Variants with 1, 3 propanediol are also common.
  • compositions of the roofing or waterproofing membranes may also contain other additives such as fillers, pigments, dyes, UV stabilizers, thermal stabilizers, fungicides, biocides, processing aids and additional plasticizers.
  • additional plasticizers are preferably low molecular weight, monomeric plasticizers such as phthalates (phthalates).
  • phthalates phthalates
  • softening agents it is also possible to use the customary plasticizers which are known from the prior art and are compatible with PVC.
  • plasticizers are, for example, derivatives of sylvic acid or acetic acid derivatives such as cumylphenyl acetate, derivatives of adipic acid such as benzyloctyl adipate, dibutyl adipate, diisobutyl adipate, di- (2-ethylhexyl) adipate, diisononyl adipate, derivatives of azelaic acid, benzoic acid derivatives, polyphenyl derivatives, citric acid derivatives, epoxidized fatty derivatives and glycol derivatives. Furthermore, it is also possible to use biobased plasticizers, ie plasticizers which contain (at least in part) renewable raw materials, as described, for example, in EP 3 156 447 A1.
  • the composition preferably contains less than 30% by weight of additional plasticizers, more preferably less than 15% by weight.
  • UV stabilizers such as oxanilides, amides, titanium dioxide, carbon black, in particular Tinuvin ® and / or Chimasorb ® and / or particularly NOR-HALS stabilizers.
  • the stabilizers are each contained in amounts of 0.01 to 10, preferably 0.1 to 5 wt .-%.
  • the total amount of stabilizers does not exceed 20% by weight of the mixture.
  • Tinuvin ® preferably Tinuvin XT 833 not only acts as a UV stabilizer but also as an acid scavenger, which improves hydrolysis.
  • the stabilizer Tinuvin XT 833 additionally captures the hydrochloric acid and improves the aging behavior as well as the hydrolysis stability.
  • Tinuvin XT 833 is listed in accordance with the safety data sheet as a product with a content of 40-60% by weight of CAS No .: 25973-55-1, whereby the chemical name is deposited as follows: 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol. Accordingly, substances which correspond to the composition of the Tinuvin XT 833 but are also listed under other product names can also be used.
  • the webs can contain the usual fillers known from the prior art, such as, for example, chalk, talc, silicas or kaolin as filler.
  • the amount of fillers is 0 to 15, preferably 1 to 10 wt .-%.
  • Chalk is preferably used as coated chalk.
  • Kaolin improves both abrasion resistance and media resistance.
  • Kaolin also has an acidic character, which can be described by means of pH, for example: here the average pH is between 4.5 and 6.5. By comparison, acetic acid has a pH of 4.75. Accordingly, in one application, the use of chalk, especially coated chalk, is preferred in order to keep the acid content in the formulation low.
  • lubricants such as lubricants, processing aids, gelling aids, UV transducers, UV stabilizers or biocides such as thiazoline derivatives, tributyltin, chloroisothiazoline, particularly preferred are isothiazoline derivatives.
  • the roof or geomembrane may also have a fiber reinforcement.
  • This fiber reinforcement can consist of a fleece, a scrim and / or a fabric.
  • the fiber reinforcement may consist of fibers which are selected from glass, mineral, polyester, polyamide, polyethylene, polypropylene fibers or mixtures of these.
  • the roofing or waterproofing membrane has an inner insert or reinforcement.
  • the roofing or Dichrungsbahn can be equipped at least on one side with a cold self-adhesive layer.
  • the roofing or waterproofing membrane may be coated on at least one side with a pressure-sensitive adhesive.
  • a pressure-sensitive adhesive In this case, the known pressure-sensitive adhesive systems come into question, in particular acrylate adhesives or adhesives based on polyurethane or else bituminous self-adhesive compositions.
  • the cold self-adhesive coating or the pressure-sensitive adhesive on both sides of the roofing or waterproofing membrane.
  • the invention also relates to a process for producing a starting mixture for producing a sealing web comprising the process steps
  • At least one carbodiimide selected from the group consisting of monomeric aliphatic carbodiimides, oligomeric aliphatic carbodiimides, polymeric aliphatic carbodiimides, monomeric aromatic carbodiimides, oligomeric aromatic carbodiimides and polymeric aromatic carbodiimides and polyester-based plasticizers,
  • composition Adding the composition to a base polymer selected from the group consisting of polyvinyl chloride, polyvinyl chloride copolymer or a reaction mixture for the preparation of the base polymer selected from polyvinyl chloride and polyvinyl chloride copolymer.
  • a base polymer selected from the group consisting of polyvinyl chloride, polyvinyl chloride copolymer or a reaction mixture for the preparation of the base polymer selected from polyvinyl chloride and polyvinyl chloride copolymer.
  • a plasticizer may also be a monomeric plasticizer.
  • the invention also provides the use of a composition comprising at least one carbodiimide selected from the group consisting of monomeric aliphatic carbodiimides, oligomeric aliphatic carbodiimides, polymeric aliphatic carbodiimides, monomeric aromatic carbodiimides, oligomeric aromatic carbodiimides, polymeric aromatic carbodiimides and at least one polyester plasticizer as plasticizer for polyvinyl chloride or polyvinyl chloride copolymer.
  • a thermal stabilizer a combination with at least one hydrotalcite can be used, which limits the water imme and additionally achieves an improvement in the hydrolytic stability.
  • the invention also provides a process for producing a roofing or sealing membrane comprising a base polymer, an ester-based polymer plasticizer and at least one hydrolysis stabilizer comprising at least one carbodiimide, wherein the hydrolysis stabilizer is incorporated into the ester-based polymer plasticizer.
  • the invention also provides a process for producing a roofing or sealing membrane comprising a base polymer, an ester-based polymer plasticizer, a high molecular weight glycidyl ester, such as epoxidized soybean oil and at least one hydrolysis stabilizer containing at least one carbodiimide, wherein the hydrolysis stabilizer in the high molecular weight glycidyl ester, such as epoxidized soybean oil is Lucasarb.
  • hydrochloric acid (HCl) release depends on the oxirane content of the high molecular weight glycidyl ester or the epoxidized soybean oil.
  • a material is selected for a standard ESBO (epoxidized soybean oil), which has the highest possible oxirane content.
  • an epoxidized soybean oil or a high molecular weight glycidyl ester is selected with a high oxirane content.
  • the oxirane content should be between 5 and 12% by weight, preferably between 8 and 11% by weight, in particular> 9% by weight.
  • a homogenized final mixture is prepared by mixing the two components. Since ester-based polymer plasticizers and high molecular weight glycidyl esters, such as epoxidized soybean oil, are higher viscosity liquids, mixing should be done in a high temperature stirred tank. The temperatures should be in the range between 50 and 100 ° C, preferably between 70 and 90 ° C. Furthermore, it is preferable to mix the liquid hydrolysis stabilizer into the higher viscosity liquid, i. into the polymer softener into the agitator with stirring. This should already be set to temperature before, which leads to a lower-viscosity liquid and thus better transportability. Subsequently, the temperature of the polymer plasticizer is kept constant by the frictional energy during the stirring process as well as via heatable stirred container walls in order to be able to perform an optimal mixing of the hydrolysis stabilizer.
  • the ratio of higher viscosity liquid (polymer plasticizer and / or epoxidized soybean oil) to liquid hydrolysis stabilizer can be varied in proportion.
  • a ratio of 3: 1 i. an addition of 4% by weight corresponds to an addition of 3% by weight of highly viscous liquid and 1% by weight of liquid hydrolysis stabilizer.
  • the invention also provides a process for producing a roofing membrane comprising a base polymer, an ester-based polymer plasticizer and at least a hydrolysis stabilizer containing at least one carbodiimide, wherein the hydrolysis stabilizer is added: the final mixture for producing the roofing membrane or
  • the final mixture zussendem one-pack stabilizer, wherein the hydrolysis stabilizer is preferably incorporated in liquid form.
  • the compounding or dry blending mixture of PVC formulations is well known to those skilled in the art and is e.g. In the following report, "Industrial Compounding Technology of Rigid and Plasticized PVC" by W. Henschel and P. Franz (PVC Technology, Fourth Edition 1984, WV Titow) has been extensively described in Compounding for soft PVC articles mostly a heating-cooling-mixer combination is used.
  • All solids i. the base polymer and other additives of solid component e.g. Fillers and pigments are added together in the hot mixer and pre-mixed for a period of about 1 to 1, 5 minutes.
  • the recipe is then added the first half of the plasticizer and mixed to a temperature of 70 to 90 ° C.
  • the second half of the plasticizer is then added to the heating mixer and heated to a temperature of e.g. 110 to 185 ° C mixed to obtain a dry final mixture.
  • the mixture is transferred to the cooling mixer and cooled down to a lower temperature preferably 40 to 60 ° C.
  • softening-resistant products such as e.g. Acrylates and / or rubbery polymers are added.
  • processing temperatures of 5 to 10 ° C higher temperature than the final temperature of the mixture is selected.
  • mixing procedure described can be used, for example, for mixing the following:
  • composition (Zi) a mixture preparation for the following composition (Zi) may be mentioned:
  • the solids ie PVC, chalk and the pigment content in the stirred tank - db the hot mixer - are added.
  • the quantities are weighed out via a previously controlled weighing pan system and dosed accordingly. These materials are premixed for about 1 to minutes without special tempering.
  • the first half of the softening components of the first mixture is added and mixed to a temperature of 70-90 ° C the heat is formed by shearing of the individual components.
  • the second part of the plasticizing component is then added and up to a temperature of 110 to 165 ° C, preferably 1 15-130 ° C, to a homogeneous and finely dispersed Dry blend without agglomeration.
  • the Dry blend mixture is transported into the cooling mixer and cooled down there by or even water-cooled container.
  • the epoxidized soybean oil may on the one hand be added to the solid components or added on the addition of the first or second portion of the softening component.
  • the hydrolysis stabilizer can on the one hand
  • the epoxidized soybean oil e.g. by mixing with a previously connected mixing tank and this during the solid component addition or during the addition of the first or second portion of the softening component with;
  • hydrolysis stabilizer can be added directly to the solid components
  • a premix tank can be used for the softening component.
  • an acrylate of the composition is additionally added in a proportion of 5.0-15.0%.
  • This acrylate can be added both for premixing of the solid components and only at a later time during transport into the cooling mixer.
  • the second variant is preferable to prevent the softener from diffusing into the acrylate and to minimize the plasticizer uptake of the PVC accordingly.
  • the late addition of the acrylate prevents blocking and thus a limited function thereof.
  • the hydrolysis stabilizer containing at least one carbodiimide directly into the polymer plasticizer or by incorporation in epoxidized soybean oil or in the masterbatch of the mixture or in the composition based on Ca / Zn One-Pack Stabilizer, Ba / Zn
  • the liquid form is to be preferred, even if the powder form is to be selected as a constituent of the masterbatch.
  • the final mixture (end-dry-blend mixture) can be processed either directly via a twin-screw extruder or via a calender.
  • ester-based plasticizers e.g. Polyester-based polymer plasticizers endangered by acid-catalytic hydrolysis.
  • the degradation of the polymer plasticizer depends. That is, the higher the acid number of the starting product, the faster the degradation of the plasticizer takes place.
  • the acid value can be described insofar as it covers all acidic functions that can be neutralized by potassium hydroxide.
  • polyester plasticizers based on adipic acid were determined with respect to the time variation of the molecular weight distribution (molecular weight distribution) according to the gel permeation chromatography (GPC) method as a function of time.
  • GPC gel permeation chromatography
  • a polyester plasticizer of a type I polyester-based plasticizer based on adipic acid and an end-capping agent using isononanol was used whose acid number of the starting product was 0.4 mgKOH / g.
  • polyester plasticizer type II Poly-based plasticizer based on adipic acid, with an end-capping with isononanol and with a different molar ratio with respect to the composition of the diols used compared to the type II was 0.66 mgKOH / g.
  • the change in weight is also reflected accordingly in the change in the acid number. This is evident from FIG. 1, in which the acid number mgKOH / g is plotted against time.
  • the curve 10 represents the time change of the acid number of a polyester-based plasticizer based on adipic acid, to which no hydrolysis stabilizer is added.
  • the polymer plasticizer is based on adipic acid / sebacic 55.0 to 59.0 wt .-%, neopentyl glycol 12- 16 wt .-%, butanediol 15.5 to 19.5 wt .-% and isononanol 10.0 to 13.0 wt .-%.
  • the sum is 100% by weight.
  • the hydrolysis stabilizer based on carbodiimide components is added to 0.5 to 4% of one of the two mixtures.
  • the Ca / Zn OnePack thermal stabilizer system consists of hydrotalcites, calcium salts of fatty acids, zinc salts of fatty acids, antioxidants, costabilizers.
  • compatibility tests were carried out in which the samples were stored at 70 ° C and 100% humidity for predetermined times. Alternatively, these tests can also be carried out at 80 ° C and 100% humidity.
  • the values were compared in each case with a blank sample.
  • the blank sample with respect to the wet value was a sample whose weight was determined one hour after removal from the humidity chamber.
  • the dry value of the blank sample was that at which the weight of the respective sample was dried for 16 hours at 70 ° C and then conditioned for one hour to cool to room temperature.
  • samples B whose plasticizers contained the hydrolysis stabilizer according to the invention, have better results than those without hydrolysis stabilizer (A). The wet value and the dry value were reduced.
  • M n number average molecular weight
  • FIG. 3 shows the temporal change of roofing sheets of composition Z 3 which contained and did not contain a hydrolysis stabilizer with a carbodiimide (curve 18) (curve 20). Young modulus / Ei 2 modulus is plotted against the storage duration in weeks. The compatibility test was carried out at 70 ° C and 100% humidity.
  • hydrolysis stabilizer based on carbodiimide components added at 0.5 to 4.0%.
  • FIG. 4 shows the result of an outdoor weathering test.
  • web samples were cut out of extruded PVC webs.
  • the composition of the webs corresponded to the composition Z 3 , where appropriate following explanations in some samples chalk was replaced by kaolin or hydrolysis stabilizers were used.
  • the initial weight (starting weight) under laboratory environment was first determined, ie. H. at 23 ° C and 50% humidity.
  • the respective samples are first stored for one hour in the laboratory environment (30 ° C / 50% humidity) and then dried at 70 ° C for a period of 16 hours. Then the weight is determined. To determine the exact weight, an average of two weathered samples is recorded. The thus determined weight loss is applied relative to the starting weight. The results are shown in FIG. 4. In the abscissa the weathering time is plotted and in the ordinate the weight loss in% compared to the starting weight.
  • compositions of the samples assigned to each curve are as follows:
  • Curve 22 relates to a sample of composition Z 3 in which the filler chalk was included in the composition.
  • a hydrolysis stabilizer was not incorporated.
  • the chalk filler had been replaced with kaolin in the samples according to curve 24.
  • a hydrolysis stabilizer was not used. Such was incorporated into the composition according to the samples represented by the curve 26.
  • the filler was chalk. If the filler chalk was replaced by kaolin with the hydrolysis stabilizer still present, curve 28 resulted for corresponding samples. Even less weight loss was found when the hydrolysis stabilizer according to the invention had been previously incorporated into the epoxidized soybean oil, the proportion of the hydrolysis stabilizer according to the invention being 10 wt .-% based on the proportion of epoxidized soybean oil was (curve 30).
  • the natural weathering test also illustrates that when a hydrolysis stabilizer according to the invention containing at least one carbodiimide is introduced into the starting composition of a plastic roofing membrane to be produced, the hydrolysis is considerably reduced in comparison with a roofing membrane of the same composition without the hydrolysis stabilizer according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une membrane de toiture contenant un polymère de base. L'invention vise à améliorer la résistance à l'hydrolyse. À cet effet, la membrane de toiture contient un plastifiant polymère à base d'ester et au moins un stabilisateur d'hydrolyse renfermant au moins un carbodiimide.
EP18785525.9A 2017-09-22 2018-09-21 Membrane de toiture Active EP3684856B8 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20184501.3A EP3766928A1 (fr) 2017-09-22 2018-09-21 Utilisation d'une composition comprenant un carbodiimide et un plastifiant de polyester comme plastifiants pour polychlorure de vinyle et copolymères de polychlorure de vinyle

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102017122065 2017-09-22
DE102017125324.6A DE102017125324A1 (de) 2017-09-22 2017-10-27 Abdichtbahn
PCT/EP2018/075673 WO2019057926A1 (fr) 2017-09-22 2018-09-21 Membrane de toiture

Related Child Applications (2)

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EP20184501.3A Division EP3766928A1 (fr) 2017-09-22 2018-09-21 Utilisation d'une composition comprenant un carbodiimide et un plastifiant de polyester comme plastifiants pour polychlorure de vinyle et copolymères de polychlorure de vinyle
EP20184501.3A Division-Into EP3766928A1 (fr) 2017-09-22 2018-09-21 Utilisation d'une composition comprenant un carbodiimide et un plastifiant de polyester comme plastifiants pour polychlorure de vinyle et copolymères de polychlorure de vinyle

Publications (3)

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EP3684856A1 true EP3684856A1 (fr) 2020-07-29
EP3684856B1 EP3684856B1 (fr) 2024-05-29
EP3684856B8 EP3684856B8 (fr) 2024-07-10

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EP18785525.9A Active EP3684856B8 (fr) 2017-09-22 2018-09-21 Membrane de toiture
EP20184501.3A Pending EP3766928A1 (fr) 2017-09-22 2018-09-21 Utilisation d'une composition comprenant un carbodiimide et un plastifiant de polyester comme plastifiants pour polychlorure de vinyle et copolymères de polychlorure de vinyle

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EP (2) EP3684856B8 (fr)
DE (1) DE102017125324A1 (fr)
WO (1) WO2019057926A1 (fr)

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1769570A1 (de) * 1968-06-10 1971-11-04 Elastomer Ag Verfahren zur Herstellung von thermoplastisch verarbeitbaren Kunststoffgemischen auf der Basis Polyurethan-Polyvinylchlorid
AT324468B (de) 1972-02-24 1975-09-10 Andritz Ag Maschf Federnde aufhangung für spannungsführende seile
DE4318979A1 (de) 1993-06-08 1994-12-15 Basf Ag Carbodiimide und/oder oligomere Polycarbodiimide auf Basis von 1,3-Bis-(1-methyl-1-isocyanato-ethyl)-benzol, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Hydrolysestabilisator
JP3508257B2 (ja) * 1994-03-17 2004-03-22 東ソー株式会社 熱可塑性エラストマー樹脂組成物およびその製造方法
DE19821666A1 (de) 1998-05-14 1999-11-25 Basf Ag Carbodiimide auf der Basis von 1,3-Bis-(1-methyl-1-isocyanatoethyl)-benzol
WO2001006813A1 (fr) 1999-07-15 2001-01-25 Sony Corporation Amplificateur de son et procede d'amplification sonore
EP1820817A1 (fr) * 2006-02-20 2007-08-22 Sika Technology AG Film polymère résistant au biodiesel
TW201609903A (zh) * 2014-08-19 2016-03-16 巴斯夫歐洲公司 包含聚合二羧酸酯及１，２－環己烷二羧酸酯的塑化劑組成物
EP3156447B1 (fr) 2015-10-13 2024-05-01 BMI Group Danmark ApS Élément de joint
EP3383432A4 (fr) 2015-12-03 2019-08-14 Nj Sharing Network Test de sous-typage d'igg pour déterminer la transplantabilité de prélèvements tissulaires
EP3243871A1 (fr) * 2016-05-09 2017-11-15 LANXESS Deutschland GmbH Compositions de carbodiimide et d'ester, leur fabrication et utilisation lors de la stabilisation de polychlorure de vinyle
ES2786623T3 (es) * 2016-05-09 2020-10-13 Lanxess Deutschland Gmbh Composiciones que contienen carbodiimida, ésteres y PVC, su preparación y uso

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Publication number Publication date
EP3766928A1 (fr) 2021-01-20
WO2019057926A1 (fr) 2019-03-28
EP3684856B1 (fr) 2024-05-29
DE102017125324A1 (de) 2019-03-28
EP3684856B8 (fr) 2024-07-10

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